Mechanosynthesis and mechanochemical treatment of bismuth-doped vanadium phosphorus oxide catalysts for the partial oxidation of n-butane to maleic anhydride

Three Bi-doped vanadyl pyrophosphate catalysts were prepared via dihydrate route （VPD method）, which consisted of different preparation methods including mechanosynthesis, mechanochemical treatment, and the conventional reflux method. The catalysts produced by the above three methods were characterized by x-ray diffraction （XRD）, scanning electron microscopy （SEM）, and temperature programmed reduction （TPR）. Catalytic evaluation for the partial oxidation of n-butane to maleic anhydride （MA） was also carried out. The XRD patterns of all the Bi-doped catalysts showed the main peaks of pyrophosphate phase. Lower intensity peaks were observed for the mechanochemically treated Bi-doped catalyst （VPDBiMill） with two additional small peaks corresponding to the presence of a small amount of V5＋ phase. The TPR profiles showed that the highest amount of active oxygen species, i.e, V4＋–O- pair, responsible for n-butane activation, was removed from VPDBiMill. Furthermore, from the catalytic test results, the graph of selectivity to MA as a function of the conversion of n-butane demonstrated that VPDBiMill was the most selective catalyst. This suggests that the mechanochemical treatment of vanadium phosphate catalyst （VPDBiMill） is a potential method to improve the catalytic properties for the partial oxidation of n-butane to maleic anhydride.

Mechanosynthesis of Boron Nitride Nanotubes

Boron nitride nanotubes （BN-NTs） with pure hexagonal BN phase have been synthesized by heating ball-milled boron powders in flowing ammonia gas at a temperature of 1200℃. The as-synthesized products were characterized by X-ray powder diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, and electron energy loss spectroscopy （EELS）. The diameters of nanotubes are in the rage of 40-120nm and the lengths are more than 10μm. EELS result identifies that the ratio of boron and nitrogen is almost 1：1 The growth temperature is a crucial growth parameter in controlling the structure and crystalline of BN-NTs. The nanotubes grown at 1100℃ possesses of a bamboo-like structure, while as the temperature increased to 1200℃, most of the nanotubes exhibited a cylindrical structure. In addition, changing the heating time can control the size of the nanotubes. The gas atmosphere has influence on the yield of BN-NTs during heating process. When heating atmosphere was replaced by nitrogen, the yield of nanotubes was remarkably decreased.

Mechanosynthesis as a Simple Method to Obtain a Magnetic Composite (Activated Carbon/Fe3O4) for Hyperthermia Treatment

A large number of magnetic nanomaterials have been studied for their hyperthermic potential, such as iron oxide based materials. These are embedded in different matrices to improve their properties. In this paper magnetite was synthesized by the coprecipitation method and an activated carbon/magnetite composite was obtained by mechanosynthesis (400 rpm, 3 h). The samples were characterized by X-ray diffraction (XRD), vibrating sample magnetometer (VSM), IR-FT spectroscopy and Scanning Electron Microscopy (SEM). Furthermore, composite heating curves as well as hemolysis tests were performed. The composite showed a superparamagnetic behavior due to its low coercivity index (8.92 Oe) and a high saturation magnetization (40.12 emu/g). SEM images showed that the magnetite was observed on the surface of activated carbon and also the IR-FT spectra indicated that oxygenated groups on the activated carbon surface were responsible for the anchoring of magnetite in the surface, with particle sizes between 9 and 14 nm. Heating results indicated that a composite mass of 18 mg reach a temperature of 45.6&degC in a low frequency magnetic field (10.2 kA and 200 kHz). Hemolysis tests indicated that the composite is a non-hemolytic material (4.7% hemolysis). These results demonstrate that the material can be used in magnetic hyperthermia techniques for cancer treatment.

Mechanosynthesis of polymer-stabilized lead bromide perovskites:Insight into the formation and phase conversion of nanoparticles

The application of polymers to replace oleylamine(OLA)and oleic acid(OA)as ligands for perovskite nanocrystals is an effective strategy to improve their stability and durability especially for the solution-based processing.Herein,we report a mechanosynthesis of lead bromide perovskite nanoparticles(NPs)stabilized by partially hydrolyzed poly(methyl methacrylate)(h-PMMA)and highmolecular-weight highly-branched poly(ethylenimine)(PEI-25K).The as-synthesized NP solutions exhibited green emission centered at 516 nm,possessing a narrow full-width at half-maximum of 17 nm and as high photoluminescence quantum yield(PL QY)as 85%,while showing excellent durability and resistance to polar solvents,e.g.,methanol.The colloids of polymer-stabilized NPs were directly processable toform stable and strongly-emitting thin films and solids,making them attractive as gain media.Furthermore,the roles of h-PMMA and PEI-25K in the grinding process were studied in depth.The h-PMMA can form micelles in the grinding solvent of dichloromethane to act as size-regulating templates for the growth of NPs.The PEI-25K with large amounts of amino groups induced significant enrichment of PbBr_(2)in the reaction mixture,which in turn caused the formation of CsPb_(2)Br_(5)-mPbBr_(2)and CsPbBr_(3)-Cs_(4)PbBr_(6)-nCsBr NPs.The presence of CsPbBr_(3)-Cs_(4)PbBr_(6)-nCsBr NPs was responsible for the high PL QY,as the Cs_(4)PbBr_(6)phase with a wide energy bandgap can passivate the surface defects of the CsPbBr_(3)phase.This work describes a direct and facile mechanosynthesis of polymer-coordinated perovskite NPs and promotes in-depth understanding of the formation and phase conversion for perovskite NPs in the grinding process.

Low-temperature Synthesis of Belite Cement from Reactive Mixtures Based on Coal Fly Ash

This paper summarizes the selected results of an extensive investigation of application of two methods （hydrothermal and mechanochemical） assisted by calcination for synthesizing belite cement from reactive mixtures （CaO/SiO2 molar ratio of 2） consisting of various waste kinds from fluidized brown coal combustion in Slovakian power plant and CaO addition. Based on XRD diffraction patterns and infrared spectra ofpre-treatment products, the formation of the new profiles corresponding to CSH phases with low degree of ordering as belite precursors after hydrothermal treatment as well as metastables calcium silicates and aluminosilicates in mechanosynthesized products was confirmed. Calcination of hydrothermally treated products led to transformation of CSH phases to wollastonite （CS）, belite and gehlenite phase, whereas creation oft^- and I^-C2S or wollastonite in milled reactive mixture took place. Differences in phase composition of products before and after calcination depend upon waste quality and precursor＇s synthesis conditions. Bottom ash isn＇t suitable as raw material for synthesizing belite phase because of high CaO content fixed in anhydrite form （44.1%）. Coal fly ash with low CaO content in anhydrite form （4.2%） and its mechanochemical or hydrothermal treatment in combination with subsequent heating offer opportunities for the utilization of coal fly ash as raw material for belite production.

Solvent-Free Mechanochemical Deprotection of N-Boc Group

Boc protection group could be readily removed in a very mild mechanochemical conditions. In a short reaction time, ball milling of Boc-protected amines with p-toluenesulfonic acid in solvent-free conditions affords corresponding amine p-TsOH salts.